KR20200050968A - Composition, film, method for forming film, and method for manufacturing patterned substrate - Google Patents

Abstract

It is an object of the present invention to provide a composition capable of forming a film excellent in flatness, wet peeling resistance and pattern bending resistance while maintaining solvent resistance, a film, a method for forming a film, and a method for manufacturing a patterned substrate. The present invention is a composition containing a compound having a group represented by the following formula (1), a molecular weight of 200 or more, a content of carbon atoms of 40 mass% or more, and a solvent. In the following formula (1), R ¹ and R ² are each independently a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or these groups are combined with each other It is part of the alicyclic structure of 3 to 20 of reduced water that is composed of the carbon atoms to which they are attached. Ar ¹ is a group excluding (n + 3) hydrogen atoms from arenes or heteroarenes of reduced water 6 to 20. X is an oxygen ^{atom, -CR 3 R 4 -, -CR} 3 R 4 -O- , or -O-CR ³ R ⁴ - a.

Description

Composition, film, method for forming film, and method for manufacturing patterned substrate

The present invention relates to a composition, a film, a method of forming a film and a method of manufacturing a patterned substrate.

In the manufacture of semiconductor devices, a multilayer resist process is used to obtain high integration. In this process, first, a composition for forming a resist underlayer film is coated on at least one side of the substrate, and then, by heating the obtained coating film, a resist underlayer film is formed, and a resist composition or the like on the side opposite to the substrate of the resist underlayer film is applied. To form a resist pattern. Subsequently, the resist underlayer film is etched using this resist pattern as a mask, and the substrate is further etched using the obtained resist underlayer film pattern as a mask, thereby forming a desired pattern on the substrate and obtaining a patterned substrate. The resist underlayer film used in such a multilayer resist process requires general properties such as solvent resistance.

In addition, in recent years, the case of forming a pattern on a plurality of types of trenches, especially substrates having trenches having different aspect ratios, has increased. In this case, the composition for forming a resist underlayer film is required to sufficiently fill these trenches and to form a film having high flatness. In response to these demands, various studies have been conducted on structures such as polymers contained in the composition for forming a resist underlayer film and functional groups contained therein (see Japanese Patent Laid-Open No. 2004-177668).

In addition, in the manufacture of an actual semiconductor device, reprocessing may be performed when a problem occurs when a silicon-containing film is formed on a substrate or when a resist film is patterned. When the film to be removed is a silicon-containing film during re-processing, a method of removing the silicon-containing film is proposed to perform a wet peeling treatment with a basic solution (International Publication Nos. 2015/146524 and Japanese Patent Publication No. 2017-92433). Reference). At this time, when a resist underlayer film is provided between the substrate and the silicon-containing film, the resist underlayer film is required to have wet peel resistance against the basic liquid.

In addition, in recent years, with the progress of miniaturization of the substrate pattern to be formed, the resist underlayer film has little curvature when etching the substrate using the formed underlayer film pattern as a mask, and it is also required to have excellent bending resistance.

Japanese Patent Publication No. 2004-177668 International Publication No. 2015/146524 Japanese Patent Publication No. 2017-92433

However, with the above-mentioned conventional composition, these demands could not be sufficiently satisfied.

The present invention has been made on the basis of the above circumstances, the purpose of which is to maintain a solvent resistance while maintaining a flatness, wet peel resistance, and a pattern capable of forming a film excellent in bending resistance, a film, a film forming method and patterning It is to provide a method of manufacturing a substrate.

The invention made to solve the above problems has a group represented by the following formula (1) (hereinafter also referred to as "group (I)"), a molecular weight of 200 or more, a carbon atom content of 40% by mass or more It is a composition containing (hereinafter, also referred to as "[A] compound") and a solvent (hereinafter, also referred to as "[B] solvent").

(In formula (1), R ¹ and R ² are each independently a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or these groups are combined with each other) These are part of the alicyclic structure of reduced water 3 to 20 composed of the carbon atom to which they are attached Ar ¹ is a group excluding (n + 3) hydrogen atoms from arenes or heteroarene of reduced water 6 to 20. X is an oxygen atom ^{, -CR 3 R 4 -, -CR} 3 R 4 -O- , or -O-CR ³ R ⁴ -. a R ³ and R ⁴ are, each independently, a hydrogen atom, a fluorine atom, a C 1 -C 20 monovalent It is a hydrocarbon group or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or these groups are part of an alicyclic structure of reduced water 3 to 20 composed of carbon atoms to which they are bonded to each other, where n is an integer from 0 to 9. n If a person, R ⁵ is a hydroxy group, to A gen atom, a nitro group or a monovalent organic group having 1 to 20 carbon atoms. N not less than 2, a plurality of R ⁵ are the same or different and are a hydroxy group, a halogen atom, a nitro group, or a monovalent group having 1 to 20 carbon atoms with each other It is an organic group or is a part of a ring structure of reduced water 4 to 20 composed of two or more of R ⁵ combined with an atomic chain to which they are bonded. * Is the formula (1) in the above [A] compound ) Indicates a binding site with a portion other than the group.)

Another invention made to solve the above problems is a film formed from the composition.

Another invention made to solve the above problems is a step of coating a composition containing the compound [A] and the solvent [B] on at least one side of the substrate (hereinafter also referred to as "the coating step (I)"). , It is a method of forming a film (hereinafter also referred to as a "film forming method (I)") including a process of heating the coated film formed by the coating process (I) (hereinafter also referred to as "heating process (I)").

Another invention made to solve the above problems is a step of coating a composition containing the compound [A] and the solvent [B] on at least one side of the substrate (hereinafter also referred to as "the coating step (II)"). , A film forming method (hereinafter referred to as a "film forming method (II)") comprising a step of heating the coated film formed by the coating process (II) at a temperature of 300 DEG C or higher (hereinafter also referred to as "heating process (II)") It is also called).

Another invention made to solve the above problems is a step of coating a composition containing a compound [A] and a solvent [B] on at least one side of a substrate (hereinafter also referred to as a "coating step (III)"). , The process of heating the coating film formed by the coating process (III) (hereinafter also referred to as "heating process (III)"), and silicon contained on the side opposite to the substrate of the film formed by the heating process (III) Patterning comprising a process of forming a film (hereinafter also referred to as a "silicon-containing film forming process (I)") and a process of removing the silicon-containing film by a basic liquid (hereinafter also referred to as a "silicon-containing film removal process") It is a manufacturing method of a substrate (hereinafter also referred to as "the manufacturing method of a patterned substrate (I)").

Another invention made to solve the above problems is a step of coating a composition containing the compound [A] and the solvent [B] on at least one side of the substrate (hereinafter also referred to as "the coating step (IV)"). , The process of heating the coating film formed by the coating process (IV) (hereinafter also referred to as "heating process (IV)"), and silicon contained on the side of the film formed by the heating process (IV) opposite to the substrate A process of forming a film (hereinafter also referred to as a "silicon-containing film forming process (II)"), and a process of forming a resist pattern on a side opposite to the substrate of the silicon-containing film (hereinafter, referred to as a "resist pattern forming process (II) ) '' And a process of performing etching using the resist pattern as a mask (hereinafter also referred to as "etching process (II)") (hereinafter referred to as "a method of manufacturing a patterned substrate") (II) Also do).

The composition of the present invention can form a film excellent in flatness, wet peeling resistance and pattern bending resistance while maintaining solvent resistance. The film of the present invention is excellent in flatness, wet peeling resistance and bending resistance of the pattern while maintaining solvent resistance. According to the film forming method of the present invention, a film excellent in flatness, wet peeling resistance and pattern bending resistance can be formed while maintaining solvent resistance. According to the method for manufacturing a patterned substrate of the present invention, a good patterned substrate can be obtained by using the formed excellent film. Therefore, these can be suitably used for the manufacture of semiconductor devices, etc., which are expected to be further refined in the future.

1 is a schematic cross-sectional view for explaining a method for evaluating flatness.
2 is a schematic plan view for explaining a method for evaluating flexural resistance.

<Composition>

The composition contains the [A] compound and the [B] solvent. The said composition may contain arbitrary components in the range which does not impair the effect of this invention. Hereinafter, each component is demonstrated.

<[A] compound>

The compound [A] is a compound having a group (I), a molecular weight of 200 or more, and a content of carbon atoms of 40 mass% or more. [A] The compound may have one group (I) or may have two or more groups (I). [A] The compound may be used alone or in combination of two or more.

By having the [A] compound, the composition can form a film excellent in flatness, wet peeling resistance and bending resistance of the pattern while maintaining solvent resistance. Although the reason why the said composition exhibits the said effect by providing the said structure is not necessarily clear, it can estimate as follows, for example. That is, it is considered that the [A] compound is not crosslinked and curing does not occur unless the temperature is relatively high, so that the fluidity of the composition can be maintained before curing. Therefore, it is considered that the flatness of the formed film is improved. Furthermore, [A] compounds, -CR ¹ R ² to the oxygen atom bonded to the ring of the arene or heterocyclic arene of Ar ¹ - has a structure adjacent groups. Even when heated at a high temperature, this structure is relatively hard to undergo oxidative decomposition. Therefore, in the formed film, the formation of phenolic hydroxyl groups is suppressed, and as a result, it is considered that the resistance to wet peeling to the basic liquid is improved. Moreover, it is thought that the bending resistance of a pattern improves because the [A] compound has the structure mentioned above, and the intensity | strength increases suitably.

[Group (I)]

The group (I) is a group represented by the following formula (1).

In the formula (1), R ¹ and R ² are each independently a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or these groups are combined with each other It is part of the alicyclic structure of 3 to 20 of reduced water that is composed of the carbon atoms to which they are attached. Ar ¹ is a group excluding (n + 3) hydrogen atoms from arenes or heteroarenes of reduced water 6 to 20. X is an oxygen ^{atom, -CR 3 R 4 -, -CR} 3 R 4 -O- , or -O-CR ³ R ⁴ - a. R ³ and R ⁴ are each independently a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or these groups are combined with each other to form a carbon atom to which they are bonded. It is a part of the alicyclic structure of the reduced water 3-20 comprised. n is an integer from 0 to 9. When n is 1, R ⁵ is a hydroxy group, a halogen atom, a nitro group, or a monovalent organic group having 1 to 20 carbon atoms. When n is 2 or more, a plurality of R ^{5 s} are the same or different from each other, and are a hydroxy group, a halogen atom, a nitro group, or a monovalent organic group having 1 to 20 carbon atoms, or two or more of the plurality of R ^5s are combined with each other to give them It is a part of the ring structure of reduced water 4 to 20 which is composed together with the bonding atom chain. * Represents the binding site with the part other than group (I) in the said [A] compound. Incidentally, "organic group" refers to a group containing at least one carbon atom.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ to R ⁴ include, for example, alkyl groups such as methyl group, ethyl group, propyl group, butyl group and pentyl group, alkenyl groups such as ethenyl group, propenyl group and butenyl group. , Chain hydrocarbon groups such as alkynyl groups such as ethynyl group, propynyl group, butynyl group, cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloalkenyl groups such as cyclopentenyl group, cyclohexenyl group, nor Alicyclic hydrocarbon groups such as a crosslinked ring hydrocarbon group such as a carbonyl group, adamantyl group, aryl groups such as a phenyl group, tolyl group, xylyl group, naphthyl group, aralkyl groups such as benzyl group, phenethyl group, and naphthylmethyl group; And aromatic hydrocarbon groups.

Examples of the monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ to R ⁴ include, for example, a group in which part or all of the hydrogen atoms of the monovalent hydrocarbon group of R ¹ to R ⁴ are substituted with fluorine atoms. Can be.

Examples of the ring structure of reduced water 3 to 20 constituting the group of R ¹ to R ⁴ include, for example, cycloalkane structures such as cyclopropane structure, cyclopentane structure, cyclohexane structure, norbornane structure, adamantane structure, and the like. And crosslinked structures.

As R ¹ and R ² , a hydrogen atom, a fluorine atom or an alkyl group is preferable.

Examples of the arnes having 6 to 20 of reducing water to which Ar ¹ is given include benzene, naphthalene, anthracene, phenanthrene, tetracene, pyrene, triphenylene, and perylene. Of these, benzene or naphthalene is preferred, and benzene is more preferred.

Examples of the heteroarene having 6 to 20 of reducing water to give Ar ¹ include pyridine, quinoline, isoquinoline, indole, pyran, benzopyran, benzofuran, and benzothiophene.

The oxygen atom and the group represented by X bonded to Ar ¹ in the formula (1) are each bonded to carbon atoms adjacent to each other in the aromatic ring of Ar ¹ .

As X, an oxygen atom or -CR ³ R ⁴ -O- is preferable, and an oxygen atom is more preferable.

As R ³ and R ⁴ , a hydrogen atom is preferable.

Examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ⁵ include, for example, a monovalent hydrocarbon group having 1 to 20 carbon atoms, between carbon-carbon of the hydrocarbon group, or between the hydrocarbon group and the atom to which R ⁵ is bonded. The group (a) containing a pseudo hetero atom-containing group, the group which substituted part or all of the hydrogen atom of the said hydrocarbon group and group ((alpha)) with a monovalent hetero atom containing group, etc. are mentioned.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include the same groups as the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ to R ⁴ described above.

Examples of the divalent hetero atom-containing group include -CO-, -CS-, -NH-, -O-, -S-, and combinations thereof.

Examples of the group (α) containing a divalent hetero atom-containing group between the carbon-carbon of the hydrocarbon group or between the hydrocarbon group and the atom to which R ⁵ is bonded, for example

Hetero atom-containing chains such as oxoalkyl groups, thioalkyl groups, alkylaminoalkyl groups, alkoxyalkyl groups, and alkylthioalkyl groups,

Hetero atom-substituted alicyclic groups such as oxocycloalkyl groups and thiocycloalkyl groups,

Aliphatic heterocyclic groups such as azacycloalkyl groups, oxacycloalkyl groups, thiacycloalkyl groups, oxocycloalkenyl groups, and oxathiacycloalkyl groups;

And aromatic heterocyclic groups such as heteroaryl groups such as pyrrolyl group, pyridyl group, quinolyl group, isoquinolyl group, furyl group, pyranyl group, thienyl group, and benzothiophenyl group.

As a monovalent hetero atom containing group, a hydroxyl group, a sulfanyl group, a cyano group, a nitro group, a halogen atom etc. are mentioned, for example.

As n, 0-3 are preferable, 0-2 are more preferable, 0 or 1 is still more preferable, and 0 is especially preferable.

Examples of the ring structure of 4 to 20 of reduced water constituting two or more of the plurality of R ⁵ include, for example, alicyclic structures such as cyclohexane structure and cyclohexene structure, and aliphatic heterocyclic structures such as azacyclohexane structure and azacyclohexene structure. , Aromatic heterocyclic structures such as an aromatic ring structure such as a benzene structure and a naphthalene structure, and a pyridine structure.

As the lower limit of the number of groups (I) of the compound [A], 2 is preferable, and 3 is more preferable. As an upper limit of the said number, 6 is preferable and 5 is more preferable. By setting the number of groups (I) in the compound (A) within the above range, the degree of crosslinking in the formed film is increased, and the curability of the composition is further improved.

Examples of the compound [A] include compounds represented by the following formula (2) (hereinafter referred to as “compound (i)”), resins (hereinafter referred to as “resin (i)”), and the like. Hereinafter, it demonstrates in order of compound (i) and resin (i).

[Compound (i)]

Compound (i) is a compound represented by the following formula (2).

In the formula (2), R ¹ , R ² , Ar ¹ , X and n have the same meanings as in the formula (1). When n is 0, R ⁶ is a (m + k) valent organic group having 1 to 60 carbon atoms. When n is 1, R ⁵ is a hydroxy group, a halogen atom, a nitro group, or a monovalent organic group having 1 to 20 carbon atoms, and R ⁶ is a (m + k) valent organic group having 1 to 60 carbon atoms, or R ⁵ and R ⁶ is a part of the ring structure of reduced water 4 to 20, which is composed of carbon chains to which they are bonded to each other, to which they are bonded. When n is 2 or more, a plurality of R ⁵ are the same or different from each other, and are a hydroxy group, a halogen atom, a nitro group, or a monovalent organic group having 1 to 20 carbon atoms, and R ⁶ is a (m + k) valent having 1 to 60 carbon atoms. It is an organic group, or two or more of a plurality of R ⁵ are combined with each other, and is a part of a ring structure of reduced water 4 to 20 composed with an atomic chain to which they are bonded, and R ⁶ is a (m + k) valent oil having 1 to 60 carbon atoms. It is a device or a part of a ring structure of reduced water 4 to 20 composed of a carbon chain to which one or more of R ⁵ and R ⁶ are joined together to combine. m is an integer from 1 to 10. R ⁷ is a monovalent organic group having 1 to 20 carbon atoms. k is an integer from 0 to 9. However, m + k is 10 or less. When m is 2 or more, a plurality of R ¹ are the same or different from each other, a plurality of R ² are the same or different from each other, a plurality of Xs are the same or different from each other, and a plurality of Ar ^1s are the same or different from each other, or Different, and a plurality of n are the same or different from each other. When k is 2 or more, a plurality of R ⁷ are the same as or different from each other.

As a lower limit of m, 2 is preferable and 3 is more preferable. As an upper limit of m, 8 is preferable and 6 is more preferable.

Examples of the monovalent organic group of R ⁷ include, for example, that in group (I), -X-CR ¹ R ² -O- bond is not formed.

As k, 0-6 are preferable, 0-2 are more preferable, 0 or 1 is still more preferable, and 0 is especially preferable.

As a lower limit of m + k, 2 is preferable and 3 is more preferable. As an upper limit of m + k, 8 is preferable and 6 is more preferable.

Examples of the (m + k) valent organic group having 1 to 60 carbon atoms represented by R ⁶ include, for example, a (m + k) valent hydrocarbon group having 1 to 60 carbon atoms, and containing a divalent hetero atom between the carbon and carbon of the hydrocarbon group. And groups containing a group (β) containing the group, the hydrocarbon group or a part or all of the hydrogen atoms of the group (β) substituted with a monovalent hetero atom-containing group. Examples of R ⁶ include, for example, groups in which (m + k-1) hydrogen atoms are excluded from the groups exemplified as monovalent organic groups having 1 to 20 carbon atoms represented by R ⁵ .

As R ⁶ , an aliphatic hydrocarbon group having 2 to 20 carbon atoms, a group derived from arene or heteroarene, a group having an aromatic ring and a carbon atom at a benzyl position bonded to the aromatic ring, and a group other than a hydrogen atom bonding to the carbon atom, lactone A group derived from a compound or a group having 4 to 60 carbon atoms in combination thereof is preferable. The hydrogen atom of these groups in R ⁶ may be substituted with at least one of a hydroxy group, a halogen atom, a nitro group, and a cyano group.

Examples of the aliphatic hydrocarbon group having 2 to 20 carbon atoms include, for example, those having 2 to 20 carbon atoms among the chain hydrocarbon groups and alicyclic hydrocarbon groups illustrated as R ¹ to R ⁴ .

As R ⁶ , more specifically, for example, groups represented by the following formulas (1-1) to (1-6) (hereinafter also referred to as “groups (1-1) to (1-6)”), etc. Can be heard.

In the formulas (1-1) to (1-6), * represents a site that is bonded to a carbon atom on the aromatic ring of Ar ¹ in the formula (2).

In the formula (1-1), R ^A1 to R ^A4 are a hydroxy group, a halogen atom, a nitro group, or a monovalent organic group having 1 to 20 carbon atoms. n1A and n1B are integers from 0 to 3. n1C and n1D are integers from 0 to 4. m1A and m1B are integers from 1 to 4. When n1A is 2 or more, a plurality of R ^A1 are the same as or different from each other. When n1B is 2 or more, a plurality of R ^{A2 s} are the same as or different from each other. When n1C is 2 or more, a plurality of R ^A3s are the same as or different from each other. When n1D is 2 or more, a plurality of R ^A4s are the same as or different from each other. However, n1A + m1A≤4 and n1B + m1B≤4. As n1A and n1B, 0 or 1 is preferable, and 0 is more preferable. As n1C and n1D, 0 or 1 is preferable. As m1A and m1B, 1 or 2 is preferable, and 2 is more preferable.

In the formula (1-2), R ^B1 to R ^B4 are a hydroxy group, a halogen atom, a nitro group, or a monovalent organic group having 1 to 20 carbon atoms. n2A, n2B, n2C and n2D are integers from 0 to 4. m2A and m2B are integers from 1 to 5. When n2A is 2 or more, a plurality of R ^B1 are the same as or different from each other. When n2B is 2 or more, a plurality of R ^B2s are the same as or different from each other. If more than n2C is 2, a plurality of R ^B3 are the same or different from each other. When n2D is 2 or more, a plurality of R ^B4s are the same as or different from each other. However, n2A + m2A≤5 and n2B + m2B≤5. As n2A and n2B, 0 or 1 is preferable, and 0 is more preferable. 0 or 1 is preferable as n2C and n2D. As m2A and m2B, 2 or 3 is preferable.

In the formula (1-3), R ^C is a hydroxy group, a halogen atom, a nitro group, or a monovalent organic group having 1 to 20 carbon atoms. n3 is 0 or 1. m3 is 2 or 3. However, n3 + m3≤3. 0 is preferable as n3. As m3, 2 or 3 is preferable.

In the formula (1-4), R ^D is a hydroxy group, a halogen atom, a nitro group, or a monovalent organic group having 1 to 20 carbon atoms. n4 is an integer from 0 to 4. m4 is an integer from 2 to 6. When n4 is 2 or more, a plurality of R ^{D s} are the same as or different from each other. However, n4 + m4≤6. As n4, 0 or 1 is preferable and 0 is more preferable. As m4, 2, 3 or 4 is preferable, and 3 is more preferable.

In the formula (1-5), R ^E1 to R ^E7 are a hydroxy group, a halogen atom, a nitro group, or a monovalent organic group having 1 to 20 carbon atoms. n5A, n5B and n5C are integers from 0 to 2. n5D, n5E, n5F and n5G are integers from 0 to 4. m5A and m5B are integers of 1-3. When n5A is 2, a plurality of R ^E1s are the same as or different from each other. If the n5B is 2, a plurality of R ^E2 are the same or different from each other. If the n5C is 2, a plurality of R ^E3 are the same or different from each other. If more than n5D is 2, a plurality of R ^E4 is the same or different from each other. If more than n5E is 2, a plurality of R ^E5 is the same as or different from each other. When n5F is 2 or more, a plurality of R ^E6 are the same or different from each other. If more than n5G is 2, a plurality of R ^E7 are each the same or different. However, n5A + m5A≤3 and n5B + m5B≤3. As n5A, n5B and n5C, 0 or 1 is preferable, and 0 is more preferable. 0 or 1 is preferable as n5D, n5E, n5F and n5G. As m5A and m5B, 1 or 2 is preferable.

In the formula (1-6), R ^F1 and R ^F2 are a hydroxy group, a halogen atom, a nitro group, or a monovalent organic group having 1 to 20 carbon atoms. n6A and n6B are integers from 0 to 4. m6 is an integer of 2-6. When n6A is 2 or more, a plurality of R ^F1 are the same as or different from each other. If more than n6B is 2, a plurality of R ^F2 are the same or different from each other. However, n6A + m6≤6. As n6A, 0 or 1 is preferable and 0 is more preferable. As n6B, 0 or 1 is preferable. As m6, 2 or 3 is preferable and 3 is more preferable.

Examples of the monovalent organic group having 1 to 20 carbon atoms include the same groups as those exemplified by R ⁵ above.

Examples of the compound (i) include compounds represented by the following formulas (i-1) to (i-7) (hereinafter also referred to as "compounds (i-1) to (i-7)") and the like. have.

In the formulas (i-1) to (i-7), Z is each independently a group (I).

As the compound (i), compounds (i-1) to (i-7) are preferable.

The lower limit of the molecular weight of the compound [A] is 200, preferably 300, and more preferably 400. As an upper limit of the said molecular weight, 3,000 is preferable, 2,000 is more preferable, and 1,500 is still more preferable.

[Resin (i)]

Resin (i) is a resin having group (I). Examples of the resin (i) include a resin having an aromatic ring in the main chain, a resin having an aromatic ring in the side chain without having an aromatic ring in the main chain, and the like. Here, the "main chain" means the longest chain composed of atoms in the compound [A]. The "side chain" means other than the longest chain composed of atoms in the compound [A]. Resin (i) is usually a compound having two or more groups (I).

As the resin (i), if classified according to the type of the basic resin, for example, phenol resin, naphthol resin, fluorene resin, aromatic ring-containing vinyl resin, acenaphthylene resin, indene resin, arylene resin, triazine Resin, pyrene resin, fullerene resin, calix arene resin, and the like.

(Phenolic resin)

The phenol resin has a structural unit derived from a phenol compound, and the structural unit is a resin having a group (I). The phenol resin can be synthesized, for example, by forming a group (I) from the phenol structure of the resin obtained by reacting the phenol compound with an aldehyde compound using an acidic catalyst or an alkaline catalyst.

Examples of the phenol compound include phenol, cresol, xylenol, resorcinol, bisphenol A, p-tert-butylphenol, and p-octylphenol.

Examples of the aldehyde compound include aldehydes such as formaldehyde, aldehyde sources such as paraformaldehyde and trioxane.

(Naphthol resin)

The naphthol resin has a structural unit derived from a naphthol compound, and the structural unit is a resin having a group (I). The naphthol resin can be synthesized, for example, by forming a group (I) from the naphthol structure of the resin obtained by reacting the naphthol compound with an aldehyde compound using an acidic catalyst or an alkaline catalyst.

Examples of the naphthol compound include α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene.

(Fluorene resin)

The fluorene resin has a structural unit derived from a fluorene compound, and the structural unit is a resin having a group (I). The fluorene resin can be synthesized, for example, by forming a group (I) from the hydroxyaryl structure of the resin obtained by reacting a fluorene compound having a hydroxyaryl structure with an aldehyde compound using an acidic catalyst or an alkaline catalyst. have.

As the fluorene compound, for example, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-hydroxyphenyl) fluorene, 9,9-bis (6-hydroxynaphthyl ) Fluorene and the like.

(Aromatic ring-containing vinyl resin)

The aromatic ring-containing vinyl resin has a structural unit derived from a compound having an aromatic ring and a polymerizable carbon-carbon double bond, and the structural unit is a resin having a group (I). The aromatic ring-containing vinyl resin is synthesized, for example, by forming a group (I) from a phenol structure of a resin having a structural unit derived from a compound having an aromatic ring having a phenolic hydroxyl group and a polymerizable carbon-carbon double bond. Can be.

(Acenaphthylene resin)

The acenaphthylene resin has a structural unit derived from an acenaphthylene compound, and the structural unit is a resin having a group (I). The acenaphthylene resin can be synthesized, for example, by forming a group (I) from a phenol structure of a resin having a structural unit derived from an acenaphthylene compound having a hydroxyaryl structure.

(Indene resin)

The indene resin has a structural unit derived from an indene compound, and the structural unit is a resin having a group (I). The indene resin can be synthesized, for example, by forming a group (I) from a hydroxyaryl structure of a resin having a structural unit derived from an indene compound having a hydroxyaryl structure.

(Arylene resin)

The arylene resin is a resin having an arylene skeleton having group (I). The arylene resin can be synthesized, for example, by forming a group (I) from the phenol structure of a resin having an arylene skeleton having a hydroxyaryl structure. As an arylene skeleton, a phenylene skeleton, a naphthylene skeleton, a biphenylene skeleton, etc. are mentioned, for example.

(Triazine resin)

The triazine resin is a resin having a triazine skeleton having group (I). The triazine resin can be synthesized, for example, by forming a group (I) from the phenol structure of a resin having a triazine skeleton having a hydroxyaryl structure.

(Pyrene resin)

The pyrene resin is a resin having a pyrene skeleton having group (I). A pyrene resin can be synthesized, for example, by forming a group (I) from a phenol structure of a resin having a pyrene skeleton having a hydroxyaryl structure. The resin having a pyrene skeleton having a hydroxyaryl structure is, for example, a resin obtained by reacting a pyrene compound having a phenolic hydroxyl group with an aldehyde compound using an acidic catalyst.

(Fullerene resin)

The fullerene resin is a resin having a fullerene skeleton having group (I). The fullerene resin can be synthesized, for example, by forming a group (I) from the phenol structure of a resin having a fullerene skeleton having a hydroxyaryl structure.

[A] When the compound is a phenol resin, naphthol resin, fluorene resin, aromatic ring-containing vinyl resin, acenaphthylene resin, indene resin, arylene resin, triazine resin, pyrene resin or fullerene resin, [A] compound As a lower limit of the weight average molecular weight (Mw), 500 is preferable, and 1,000 is more preferable. Moreover, as an upper limit of the said Mw, 50,000 is preferable, 10,000 is more preferable, and 8,000 is still more preferable.

The lower limit of the ratio (Mw / Mn) to the number average molecular weight (Mn) of the Mw of the [A] compound is usually 1, and 1.1 is preferable. As an upper limit of the said Mw / Mn, 5 is preferable, 3 is more preferable, and 1.5 is still more preferable.

[A] For the Mw and Mn of the compound, Tosoh Corporation's GPC columns (two "G2000HXL" and one "G3000HXL") were used, flow rate: 1.0 mL / min, elution solvent: tetrahydrofuran, column temperature: It is a value measured by gel permeation chromatography (detector: Differential Refractometer) based on monodisperse polystyrene under analytical conditions of 40 ° C.

(Calix arene resin)

The calix arene resin is a cyclic oligomer having a group (I) in which a plurality of cyclic bonds of aromatic rings to which a phenolic hydroxyl group is bonded are via a hydrocarbon group.

Examples of the calix arene resin include resins having a structure represented by the following formula (1-7) (hereinafter referred to as "calix arene resin (i)") and the like.

In the formula (1-7), R ^G1 is a hydroxyl group or -OR ^G2 . R ^G2 is a monovalent organic group having 1 to 20 carbon atoms. R ^G3 , R ^G4 and R ^G5 are hydroxy groups, halogen atoms, nitro groups or monovalent organic groups having 1 to 20 carbon atoms. n7A, n7B, n7C and n7D are integers from 0 to 3. When n7A is 2 or more, a plurality of R ^G1 are the same as or different from each other. When R ^G2 is plural, plural R ^G2 are the same or different from each other. When n7B is 2 or more, a plurality of R ^G3s are the same as or different from each other. When n7C is 2 or more, a plurality of R ^G4s are the same as or different from each other. When n7D is 2 or more, a plurality of R ^G5s are the same as or different from each other. As n7A, n7B, n7C and n7D, 0, 1 or 2 is preferable. * Represents the site | part which couple | bonds with the carbon atom on the aromatic ring of Ar ¹ of said formula (2).

Examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ^G2 to R ^G5 include groups similar to those exemplified as the monovalent organic group for R ⁵ .

Examples of the resin having a structure represented by the formula (1-7) include resins represented by the following formulas (i-8) and (i-9).

In the formulas (i-8) and (i-9), Z is each independently a group (I).

When the compound [A] is a calix arene resin, as the lower limit of its molecular weight, from the viewpoint of further improving the flatness of the composition, 500 is preferred, 700 is more preferred, and 1,000 is even more preferred. As an upper limit of the said molecular weight, 5,000 is preferable, 3,000 is more preferable, 2,000 is more preferable, and 1,500 is especially preferable.

[Synthesis method of [A] compound]

The compound [A] can be synthesized, for example, by using the respective precursor compounds having groups (I), and performing reactions shown in the following (a) to (d).

(a) a phenol compound having a group (I) such as sesamol, a dihalo aromatic compound such as 2,6-difluorobenzonitrile, 5,5 ', 6,6'-tetrahydroxy-3, Dehalogenated hydrogen condensation in a solvent such as N, N-dimethylacetamide in the presence of a base such as potassium carbonate using a polyhydric phenol compound such as 3,3 ', 3'-tetramethyl-1,1-spirobisindan Compound (i) is obtained by performing reaction.

(b) Using an acetophenone compound having a group (I) such as 3,4- (methylenedioxy) acetophenone, in the presence of an acid such as dodecylbenzenesulfonic acid, a trimerization reaction in a solvent such as m-xylene By carrying out, compound (i) having a benzene skeleton is obtained.

(c) a compound containing a carbon-carbon double bond-containing group having a group (I) such as 5-vinyl-1,3-benzodioxole, and in the presence of a polymerization initiator such as 2,2-azobisisobutyrate. , Resin (i) is obtained by performing polymerization reaction in a solvent such as methyl ethyl ketone.

(d) Carlyx by using an aromatic aldehyde compound having a group (I) such as piperonal and a phenolic compound such as resorcinol, and performing a condensation reaction in a solvent such as ethanol in the presence of an acid such as hydrochloric acid The arene resin (i) is obtained.

The phenolic hydroxyl group of the synthesized compound is, for example, using an organic halide such as propargyl bromide, 4-methyl-2-pentanone, methanol, etc. in the presence of a base such as tetramethylammonium hydroxide. By performing a dehalogenated condensation reaction in a solvent of [A], the compound [A] in which another group is introduced can be obtained.

Compounds [A] other than the above-mentioned (a) to (d) can also be synthesized by the same known methods as above.

As an upper limit of the content rate of the carbon atom in [A] compound, 95 mass% is preferable, 90 mass% is more preferable, and 85 mass% is still more preferable. As a lower limit of the content rate of the said carbon atom, 40 mass% is preferable, 45 mass% is more preferable, 50 mass% is more preferable, 55 mass% is especially preferable. By making the content of the carbon atom in the [A] compound into the above range, solvent resistance can be improved.

As an upper limit of the content rate of the hydrogen atom in [A] compound, 6.5 mass% is preferable, 6.0 mass% is more preferable, 5.0 mass% is more preferable, and 4.0 mass% is especially preferable. As a lower limit of the content rate of the said hydrogen atom, it is 0.1 mass%, for example. By setting the content of hydrogen atoms in the compound [A] within the above range, the bending resistance of the resist underlayer film pattern during etching of the substrate can be further improved.

As a lower limit of the content rate of the [A] compound in the solid content of the composition, 50 mass% is preferable, 70 mass% is more preferable, and 85 mass% is more preferable. The upper limit of the content rate is, for example, 100% by mass. The "solid content" refers to components other than the [B] solvent in the composition.

As a lower limit of the content rate of the [A] compound in the composition, 1 mass% is preferable, 3 mass% is more preferable, and 5 mass% is more preferable. As an upper limit of the said content rate, 50 mass% is preferable, 30 mass% is more preferable, and 15 mass% is still more preferable.

<[B] solvent>

[B] The solvent is not particularly limited as long as it can dissolve or disperse the [A] compound and any components contained as necessary.

Examples of the solvent [B] include alcohol-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, and nitrogen-containing solvents. [B] The solvent can be used alone or in combination of two or more.

Examples of the alcohol-based solvent include monoalcohol-based solvents such as methanol, ethanol, and n-propanol; polyhydric alcohol-based solvents such as ethylene glycol and 1,2-propylene glycol.

Examples of the ketone-based solvent include chain ketone-based solvents such as methyl ethyl ketone and methyl-iso-butyl ketone, and cyclic ketone-based solvents such as cyclohexanone.

Examples of the ether-based solvent include polyether alcohol-based solvents such as chain ether-based solvents such as n-butyl ether, cyclic ether-based solvents such as tetrahydrofuran, and polyhydric alcohol partial ether-based solvents such as diethylene glycol monomethyl ether. And the like.

Examples of the ester solvent include carbonate-based solvents such as diethyl carbonate, acetic acid monoester-based solvents such as methyl acetate and ethyl acetate, lactone-based solvents such as γ-butyrolactone, and diethylene glycol monoacetate. And polyhydric alcohol partial ether carboxylate-based solvents such as methyl ether and propylene glycol monomethyl ether acetate, and lactic acid ester-based solvents such as methyl lactate and ethyl lactate.

Examples of the nitrogen-containing solvent include chain nitrogen-containing solvents such as N, N-dimethylacetamide, and cyclic nitrogen-containing solvents such as N-methylpyrrolidone.

Among these, ether-based solvents and / or ester-based solvents are preferred, and from the viewpoint of excellent film-forming properties, ether-based solvents and / or ester-based solvents having a glycol structure are more preferable.

Examples of ether-based solvents and ester-based solvents having a glycol structure include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, and propylene acetate. Glycol monopropyl ether, and the like. Among these, propylene glycol monomethyl ether acetate is particularly preferable.

[B] As the lower limit of the content of the ether-based solvent and the ester-based solvent having a glycol structure in the solvent, 20 mass% is preferable, 60 mass% is more preferable, 90 mass% is more preferable, and 100 mass% is particularly desirable.

<Optional ingredients>

The composition may contain, as an optional component, an acid generator, a crosslinking agent, a surfactant, and an adhesion aid.

[Acid generator]

The acid generator is a component that generates acid by the action of heat or light and promotes crosslinking of the [A] compound. When the composition contains an acid generator, the crosslinking reaction of the [A] compound is promoted, and the hardness of the formed film can be further increased. The acid generators may be used alone or in combination of two or more.

As an acid generator, an onium salt compound, an N-sulfonyloxyimide compound, etc. are mentioned, for example.

[Crosslinking system]

The crosslinking agent is a component that forms a crosslinking bond between components such as the [A] compound in the composition, or itself forms a crosslinking structure by the action of heat or acid. When the composition contains a crosslinking agent, the hardness of the formed film can be increased. A crosslinking agent can be used individually by 1 type or in combination of 2 or more type.

Examples of the crosslinking agent include polyfunctional (meth) acrylate compounds, epoxy compounds, hydroxymethyl group-substituted phenolic compounds, alkoxyalkyl group-containing phenolic compounds, and compounds having an alkoxyalkylated amino group.

[Preparation method of composition]

The composition can be prepared by mixing the [A] compound, the [B] solvent and, if necessary, an optional component in a predetermined ratio, and preferably filtering the obtained mixture with a membrane filter having a pore diameter of 0.1 µm or less. . As a lower limit of the solid content concentration of the said composition, 0.1 mass% is preferable, 1 mass% is more preferable, 3 mass% is more preferable, and 5 mass% is especially preferable. As an upper limit of the said solid content concentration, 50 mass% is preferable, 30 mass% is more preferable, 20 mass% is more preferable, and 15 mass% is especially preferable.

Since the composition can form a film excellent in flatness, wet peeling resistance and pattern bending resistance while maintaining solvent resistance, it can be suitably used to form a resist underlayer film in the manufacture of semiconductor devices and the like.

<Mem>

The film is formed of the composition. Since the film is formed of the above-described composition, it is excellent in flatness, wet peeling resistance and bending resistance of the pattern while maintaining solvent resistance.

<How to form a film>

Examples of the method for forming the film include a film forming method (I) and a film forming method (II).

[Method of Forming Film (I)]

The film forming method (I) includes a coating step (I) and a heating step (I). According to the method (I) of forming a film, the above-described composition is used, so that a film excellent in flatness, wet peeling resistance and bending resistance of a pattern can be formed while maintaining solvent resistance. Hereinafter, each process is demonstrated.

(Coating process (I))

In this step, the composition is coated on at least one side of the substrate. Thereby, a coating film is formed.

Examples of the substrate include a silicon wafer, a wafer coated with aluminum, and the like. In addition, the coating method of the said composition is not specifically limited, For example, it can carry out by a suitable method, such as a rotation coating, a flexible coating, a roll coating, and can form a coating film by this.

(Heating process (I))

In this step, the coated film obtained in the coating step (I) is heated. Thus, a film is formed.

Although the heating of the coating film is usually performed under the atmosphere, it may be performed under a nitrogen atmosphere. As heating temperature, it is 200 to 600 degreeC, for example. The heating time is, for example, 15 seconds or more and 1,200 seconds or less.

Before heating the coating film at a temperature of 200 ° C or higher and 600 ° C or lower, preheating may be performed at a temperature of 60 ° C or higher and 150 ° C or lower. As a lower limit of the heating time in preliminary heating, 10 seconds is preferable, and 30 seconds is more preferable. As an upper limit of the said heating time, 300 second is preferable and 180 second is more preferable.

Further, in the method for forming a film (I), the coating film is heated to form a film, but when the composition contains an acid generator and the acid generator is a radiation-sensitive acid generator, the film is cured by combining exposure and heating. It is also possible to form a resist underlayer film. The radiation used for this exposure is appropriately selected from electromagnetic waves such as visible light, ultraviolet light, far ultraviolet light, X-rays, γ-rays, particle beams such as electron beams, molecular beams, and ion beams, depending on the type of acid generator.

As a lower limit of the average thickness of the formed film, 30 nm is preferable, 50 nm is more preferable, and 100 nm is more preferable. As an upper limit of the said average thickness, 3,000 nm is preferable, 2,000 nm is more preferable, and 500 nm is still more preferable.

[Method of Forming Film (II)]

The film formation method (II) includes a coating process (II) and a heating process (II). According to the method (II) for forming a film, since the above-described composition is used, it is possible to form a film excellent in flatness, wet peeling resistance and pattern bending resistance while maintaining solvent resistance. Hereinafter, each process is demonstrated.

(Coating process (II))

In this step, the composition is coated on at least one side of the substrate. Thereby, a coating film is formed. This step is the same as the coating step (I) described above.

(Heating process (II))

In this step, the coated film obtained by the coating step (II) is heated. Thus, a film is formed.

Although the heating of the coating film is usually performed under the atmosphere, it may be performed under a nitrogen atmosphere. The lower limit of the heating temperature is 300 ° C, preferably 320 ° C, and more preferably 340 ° C. As an upper limit of a heating temperature, 500 degreeC is preferable, 450 degreeC is more preferable, and 400 degreeC is still more preferable. When the heating temperature is 300 ° C or higher, it can be cured in a state having high fluidity, and flatness is further improved. As a lower limit of a heating time, 15 second is preferable, 30 second is more preferable, and 45 second is still more preferable. As an upper limit of a heating time, 1,200 second is preferable, 600 second is more preferable, and 300 second is still more preferable.

Before heating the coating film at a temperature of 300 ° C or higher and 500 ° C or lower, preheating may be performed at a temperature of 100 ° C or higher and 200 ° C or lower. As a lower limit of the heating time in preliminary heating, 10 seconds is preferable, and 30 seconds is more preferable. As an upper limit of the said heating time, 300 second is preferable and 180 second is more preferable.

In addition, in the method (II) of forming the film, the coating film is heated to form a film, but when the composition contains an acid generator and the acid generator is a radiation-sensitive acid generator, the film is formed by combining exposure and heating. It is also possible to form a resist underlayer film by curing. The radiation used for this exposure is appropriately selected from electromagnetic waves such as visible light, ultraviolet light, far ultraviolet light, X-rays, γ-rays, particle beams such as electron beams, molecular beams, and ion beams, depending on the type of acid generator.

As a lower limit of the average thickness of the formed film, 30 nm is preferable, 50 nm is more preferable, and 100 nm is more preferable. As an upper limit of the said average thickness, 3,000 nm is preferable, 2,000 nm is more preferable, and 500 nm is still more preferable.

<Method of manufacturing patterned substrate>

As a manufacturing method of the said patterned substrate, the manufacturing method (I) of a patterned substrate, the manufacturing method (II) of a patterned substrate, etc. are mentioned, for example.

[Method of manufacturing patterned substrate (I)]

The manufacturing method (I) of the patterned substrate includes a coating process (III), a heating process (III), a silicon-containing film forming process (I), and a silicon-containing film removal process.

According to the manufacturing method (I) of the patterned substrate, a film excellent in flatness, wet peeling resistance and bending resistance of the pattern is used while maintaining the solvent resistance obtained by the above-described film formation method, and thus a patterned substrate having excellent pattern shape Can get

The manufacturing method (I) of the patterned board | substrate may perform a silicon containing film formation process (I) again after the said silicon containing film removal process as needed. In addition, after the silicon-containing film forming step (I), a step of forming a resist pattern on the surface side opposite to the substrate of the silicon-containing film (hereinafter also referred to as "resist pattern forming step (I)") and a resist pattern as a mask A step of performing one etching (hereinafter also referred to as "etching step (I)") may be further provided. Hereinafter, each process is demonstrated.

(Coating process (III))

In this step, the composition is coated on at least one side of the substrate. Thereby, a coating film is formed. This step is the same as the coating step (I) described above.

(Heating process (III))

In this step, the coated film obtained in the coating step (III) is heated. Thus, a film is formed. This step is the same as the heating step (I) described above.

(Process for forming silicon-containing film (I))

In this step, a silicon-containing film is formed on the side of the film obtained in the heating step (III) opposite to the substrate.

The silicon-containing film is formed by curing the coating film formed by coating the silicon-containing film-forming composition on the side opposite to the substrate of the film, usually by exposure and / or heating. As a commercial item of the composition for forming a silicon-containing film, for example, "NFC SOG01", "NFC SOG04", "NFC SOG080" (above, JSR Corporation), or the like can be used.

Examples of the radiation used for the exposure include electromagnetic waves such as visible light, ultraviolet light, far ultraviolet light, X-rays, γ-rays, electron beams, molecular beams, and particle beams such as ion beams.

As a lower temperature limit when heating a coating film, 90 degreeC is preferable, 150 degreeC is more preferable, and 200 degreeC is still more preferable. As an upper limit of the said temperature, 550 degreeC is preferable, 450 degreeC is more preferable, and 300 degreeC is still more preferable. As a lower limit of the average thickness of the silicon-containing film to be formed, 1 nm is preferable, 10 nm is more preferable, and 20 nm is more preferable. As said upper limit, 20,000 nm is preferable, 1,000 nm is more preferable, and 100 nm is still more preferable.

(Silicon-containing film removal process)

In this step, the silicon-containing film obtained in the silicon-containing film forming step (I) is removed with a basic liquid. According to this process, the silicon-containing film can be removed without causing significant damage to the substrate and the film, and the film-equipped substrate on which the film is formed on the substrate can be reworked. It is also possible to perform a patterned or unpatterned silicon-containing film before the etching step (I) described later. That is, for example, when a problem occurs in the silicon-containing film forming step (I) or when a problem occurs in the patterned silicon-containing film before the etching step (I) described later, the film is provided by performing this step. The silicon-containing film forming step (I) can be repeated without discarding the substrate.

The method for removing the silicon-containing film is not particularly limited as long as it is a method that allows the silicon-containing film and the basic liquid to contact for a certain period of time. For example, a method of immersing a film-equipped substrate on which a silicon-containing film is formed in a basic liquid, a method of spraying a basic liquid, a method of applying a basic liquid, and the like can be given.

As said basic liquid, alkaline hydrogen peroxide water etc. are mentioned, for example. More specifically, a mixed aqueous solution of ammonia and hydrogen peroxide (25% by mass aqueous ammonia solution / 30% by mass aqueous hydrogen peroxide solution / water = 1/2/40 (mass ratio) mixed aqueous solution (SC1)) is particularly preferable. The method for removing the silicon-containing film when using alkaline hydrogen peroxide is not particularly limited as long as the silicon-containing film and the alkaline hydrogen peroxide water can be contacted for a certain period of time under heating conditions. For example, the silicon-containing film-equipped substrate is heated. And a method of immersing in alkaline hydrogen peroxide water, a method of spraying alkaline hydrogen peroxide water under a heating environment, a method of applying heated alkaline hydrogen peroxide water, and the like. After each of these methods, the substrate with a film may be washed with water and dried.

As a lower temperature limit when performing using alkaline hydrogen peroxide water, 40 degreeC is preferable and 50 degreeC is more preferable. As an upper limit of the said temperature, 90 degreeC is preferable and 80 degreeC is more preferable.

As the lower limit of the immersion time in the immersion method, 1 minute is preferable, 2 minutes are more preferable, and 3 minutes are more preferable. As an upper limit of the said time, 30 minutes are preferable and 15 minutes are more preferable.

(Resist pattern forming process (I))

In this step, a resist pattern is formed on the side of the film opposite to the substrate. As a method for performing this step, for example, a method using a resist composition and the like can be mentioned.

As a method of using the resist composition, specifically, a resist composition is formed by coating the resist composition so that the resulting resist film has a predetermined thickness, and then pre-baking to volatilize the solvent in the coating film to form a resist film.

Examples of the resist composition include a positive or negative chemically amplified resist composition containing a radiation-sensitive acid generator, a positive resist composition containing an alkali-soluble resin and a quinonediazide-based photosensitizer, and an alkali-soluble resin. And a negative resist composition containing a crosslinking agent.

As a lower limit of solid content concentration of the said resist composition, 0.3 mass% is preferable, and 1 mass% is more preferable. As an upper limit of the said solid content concentration, 50 mass% is preferable and 30 mass% is more preferable. In addition, the resist composition is generally filtered, for example, with a filter having a pore diameter of 0.2 µm or less, and provided for formation of a resist film. Moreover, in this process, a commercially available resist composition can also be used as it is.

It does not specifically limit as a coating method of a resist composition, For example, a rotation coating method etc. are mentioned. In addition, as the temperature of the pre-baking, it is appropriately adjusted depending on the kind of resist composition used and the like, but as the lower limit of the temperature, 30 ° C is preferable, and 50 ° C is more preferable. As an upper limit of the said temperature, 200 degreeC is preferable and 150 degreeC is more preferable. As a lower limit of a prebaking time, 10 second is preferable and 30 second is more preferable. As an upper limit of the said time, 600 second is preferable and 300 second is more preferable.

Subsequently, the formed resist film is exposed by selective irradiation. As radiation used for exposure, depending on the type of radiation-sensitive acid generator used in the resist composition, it can be used in electromagnetic radiation such as visible light, ultraviolet light, far ultraviolet light, X-rays, γ-rays, electron beams, molecular beams, and particle beams such as ion beams. It is selected appropriately. Among these, far ultraviolet rays are preferred, KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), F ₂ excimer laser light (wavelength 157 nm), Kr ₂ excimer laser light (wavelength 147 nm), ArKr excimer Laser light (wavelength 134 nm) or extreme ultraviolet (wavelength 13.5 nm, EUV) is more preferable, KrF excimer laser light, ArF excimer laser light or EUV is more preferable.

After the exposure, post-baking may be performed to improve resolution, pattern profile, developability, and the like. As the temperature of this post-baking, it is appropriately adjusted depending on the kind of resist composition used, and the like, and as the lower limit of the temperature, 50 ° C is preferable, and 70 ° C is more preferable. As an upper limit of the said temperature, 200 degreeC is preferable and 150 degreeC is more preferable. As the lower limit of the post-baking time, 10 seconds is preferable, and 30 seconds is more preferable. As an upper limit of the said time, 600 second is preferable and 300 second is more preferable.

Next, the exposed resist film is developed with a developer to form a resist pattern. This phenomenon may be an alkali development or an organic solvent development. As the developing solution, for alkali development, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine , Methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo [5.4.0] And basic aqueous solutions such as -7-undecene and 1,5-diazabicyclo [4.3.0] -5-nonene. To these basic aqueous solutions, water-soluble organic solvents such as alcohols such as methanol and ethanol, surfactants and the like can also be added in appropriate amounts. In addition, in the case of developing an organic solvent, examples of the developer include various organic solvents exemplified as the [B] solvent of the above-described composition.

After development with the developer, a predetermined resist pattern is formed by washing and drying.

As a method for performing the resist pattern forming process, in addition to the method using the above-described resist composition, a method using a nanoimprint method, a method using a self-organizing composition, or the like can also be used.

(Etching process (I))

In this step, etching using the resist pattern as a mask is performed. Thus, a pattern is formed on the substrate. As the number of times of etching, a single circuit may be performed multiple times, that is, a pattern obtained by etching may be sequentially etched, but from the viewpoint of obtaining a pattern with a better shape, multiple times are preferable. When a plurality of etching is performed, etching is sequentially performed in the order of the silicon-containing film, film, and substrate. Dry etching, wet etching, etc. are mentioned as a method of etching. Of these, dry etching is preferred from the viewpoint of making the pattern shape of the substrate better. A gas plasma such as oxygen plasma or the like is used for the dry etching. After the etching, a patterned substrate having a predetermined pattern is obtained.

[Method of Manufacturing Patterned Substrate (II)]

The manufacturing method (II) of the patterned substrate includes a coating process (IV), a heating process (IV), a silicon-containing film forming process (II), a resist pattern forming process (II), and an etching process (II). To be equipped.

According to the manufacturing method (II) of the patterned substrate, since a film excellent in flatness, wet peeling resistance and bending resistance of the pattern is used while maintaining the solvent resistance obtained by the above-described film forming method, a patterned substrate having an excellent pattern shape Can get Hereinafter, each process is demonstrated.

(Coating process (IV))

In this step, the composition is coated on at least one side of the substrate. Thereby, a coating film is formed. This step is the same as the coating step (I) described above.

(Heating process (IV))

In this step, the coated film obtained in the coating step (IV) is heated. Thus, a film is formed. This step is the same as the heating step (I) described above.

(Resist pattern formation process (II))

In this step, a resist pattern is formed on the side of the film opposite to the substrate. This step is the same as the resist pattern forming method (I) described above.

(Etching process (II))

In this step, etching using the resist pattern as a mask is performed. Thus, a pattern is formed on the substrate. This step is the same as the etching step (I) described above.

Example

Hereinafter, the present invention will be described more specifically by examples, but the present invention is not limited to these examples. The measurement method of various physical property values is shown below.

[Weight average molecular weight (Mw)]

[A] When the compound is a polymer, Mw is a Tosoh Corporation GPC column (two "G2000HXL" and one "G3000HXL") flow rate: 1.0 mL / min, elution solvent: tetrahydrofuran, Column temperature: Measured by gel permeation chromatography (detector: Differential Refractometer) based on monodisperse polystyrene under analytical conditions of 40 ° C.

The carbon atom content and hydrogen atom content in the [A] compound were calculated by calculation.

[Average thickness of film]

The average thickness of the film was measured using a spectroscopic ellipsometer ("M2000D" manufactured by J.A.WOOLLAM).

<Synthesis of [A] compound>

Compounds represented by the following formulas (A-1) to (A-9) (hereinafter also referred to as "compounds (A-1) to (A-9)") and the following formulas (A-10) to (A-11) ) (Hereinafter also referred to as "resin (A-10) to (A-11)") were synthesized by the procedure shown below.

[Synthesis Example 1-1]

Under nitrogen atmosphere, 30.0 g of sesamol, 28.8 g of 2,6-difluorobenzonitrile, 30.0 g of potassium carbonate, and 146.9 g of N, N-dimethylacetamide were added to the reaction vessel and reacted at 120 ° C for 7 hours. The reaction solution was then cooled to room temperature, 14.1 g of 5,5 ', 6,6'-tetrahydroxy-3,3,3', 3'-tetramethyl-1,1-spirobisindan, 17.2 g of potassium carbonate The compound (A-1) was obtained by adding 14.1 g of g and N, N-dimethylacetamide and reacting at 130 ° C for 12 hours.

[Synthesis Examples 1-2 to 1-4, 1-6 to 1-8]

The precursors were appropriately selected, and the compounds (A-2) to (A-4) and (A-6) to (A-8) were synthesized in the same manner as in Synthesis Example 1-1.

[Synthesis Example 1-5]

To the reaction vessel, under nitrogen atmosphere, 20.0 g of 3,4- (methylenedioxy) acetophenone and 20.0 g of m-xylene were added, and then 4.0 g of dodecylbenzenesulfonic acid was added and reacted at 140 ° C for 16 hours. Compound (A-5) was obtained.

[Synthesis Example 1-9]

A precursor was appropriately selected, and the compound (A-9) was synthesized in the same manner as in Synthesis Example 1-5.

[Synthesis Example 1-10]

Under a nitrogen atmosphere, 14.0 g of methyl ethyl ketone was added to the reaction vessel, and the liquid temperature was raised to 80 ° C. Separately, a solution prepared from 20.0g of 5-vinyl-1,3-benzodioxole, 1.6g of 2,2-azobisisobutyrate and 26.0g of methyl ethyl ketone was added dropwise over 3 hours while maintaining 80 ° C to the solution. . The resin (A-10) was obtained by further dropping and aging at 80 ° C for 3 hours.

[Synthesis Example 1-11]

To the reaction vessel, 15.0 g of resorcinol, 20.5 g of piperonal and 177.3 g of ethanol were added under a nitrogen atmosphere and dissolved at room temperature. 40.1 g of concentrated hydrochloric acid was added dropwise to the obtained solution over 1 hour, after which the solution temperature was set to 80 ° C and aged for 7 hours. After aging, the solution was cooled to room temperature. Thereafter, the precipitated reddish brown solid was recovered by filtration to remove the ethanol solution, thereby obtaining a solid as a precursor.

Next, 15.0 g of the obtained precursor, 30.0 g of 4-methyl-2-pentanone, 15.0 g of methanol, and 45.2 g of a 25% by mass aqueous solution of tetramethylammonium hydroxide were added to the reaction vessel under a nitrogen atmosphere and dissolved at room temperature. . Then, it heated up to 50 degreeC, 14.7 g of propargyl bromide was dripped over 30 minutes, and it was aged at 50 degreeC for 6 hours as it was, and the said resin (A-11) was obtained.

[Synthesis Example 2-1]

To the reaction vessel, under nitrogen atmosphere, 250.0 g of m-cresol, 125.0 g of 37% by mass formalin and 2 g of oxalic anhydride were added, reacted at 100 ° C for 3 hours, and at 180 ° C for 1 hour, and then unreacted monomer was removed under reduced pressure. Then, a resin represented by the following formula (a-1) was obtained. Mw of the obtained resin (a-1) was 11,000.

<Preparation of composition>

[A] Compound, [B] solvent, acid generator (hereinafter also referred to as "[C] acid generator") and crosslinking agent (hereinafter also referred to as "[D] crosslinking agent") used in the preparation of the composition are as follows. Shows.

[[A] compound]

Examples: Compounds (A-1) to (A-9), resins (A-10) and (A-11) synthesized above

Comparative Example: The synthetic resin (a-1)

[[B] solvent]

B-1: Propylene glycol monomethyl ether acetate

[[C] acid generator]

C-1: Bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate (compound represented by the following formula (C-1))

[[D] crosslinking agent]

D-1: 1,3,4,6-tetrakis (methoxymethyl) glycoluril (compound represented by the following formula (D-1))

[Example 1-1]

[A] 10 parts by mass of (A-1) as a compound was dissolved in 90 parts by mass of (B-1) as a [B] solvent. The obtained solution was filtered through a membrane filter having a pore diameter of 0.1 µm to prepare composition (J-1).

[Examples 1-2 to 1-11 and Comparative Example 1-1]

Compositions (J-2) to (J-11) and (CJ-1) were prepared in the same manner as in Example 1-1 except that each component of the type and content shown in Table 1 below was used. "-" In Table 1 indicates that the corresponding component was not used.

<Formation of film>

[Examples 2-1 to 2-11 and Comparative Example 2-1]

The prepared composition was coated on a silicon wafer (substrate) by a spin coating method using a spin coater ("CLEAN TRACK ACT12" manufactured by Tokyo Electron Co., Ltd.). Subsequently, under an atmospheric atmosphere, a film having an average thickness of 200 nm was formed on the substrate by heating (sintering) at a heating temperature (° C) and heating time (sec) shown in Table 2 below, and then cooling at 23 ° C for 60 seconds. A film-equipped substrate on which a film was formed was obtained.

<Evaluation>

The following items were evaluated by the following methods using the obtained composition and the obtained film-equipped substrate. Table 2 shows the evaluation results.

[Solvent tolerance]

The obtained film-equipped substrate was immersed in cyclohexanone (room temperature) for 1 minute. The average thickness of the membrane before and after immersion was measured. The average thickness of the film before immersion was X ₀ and the average thickness of the film after immersion was X ₁ , and an absolute value of a value obtained from (X ₁ -X ₀ ) × 100 / X ₀ was calculated, and it was referred to as a film thickness change rate (%). . The solvent resistance is "A" (good) when the film thickness change rate is less than 1%, "B" (slightly good) when 1% or more and less than 5%, and "C" (poor) when it is 5% or more. did.

[Flatness]

1, a spin coater ("CLEAN TRACK ACT12" of Tokyo Electron Co., Ltd.) was used on the silicon substrate 1 on which a trench pattern of 100 nm in depth and 10 m in width was formed, as shown in FIG. Then, it was coated by a rotation coating method. The rotation speed of the spin coat was the same as in the case of forming a film having an average thickness of 200 nm in the above-mentioned "film formation". Subsequently, under an atmospheric atmosphere, heating (firing) was performed at the heating temperature (° C) and heating time (sec) shown in Table 2 below to form a film 2 having an average thickness of 200 nm in a portion of the non-trench pattern, A silicon substrate with a film coated with the silicon substrate was obtained.

The cross-sectional shape of the silicon substrate with a film was observed with a scanning electron microscope ("S-4800" by Hitachi High-Technologies Co., Ltd.), and the height in the central portion b of the trench pattern of the film and the trench pattern The difference (ΔFT) from the height in the portion a of the bit trench pattern at a location of 5 µm from the stage of was used as an index of flatness. The flatness was evaluated as "A" (good) when this ΔFT was less than 40 nm, "B" (slightly good) when more than 40 nm and less than 60 nm, and "C" (bad) when more than 60 nm. . In addition, the difference in height shown in FIG. 1 is described to be more exaggerated than in reality.

[Wet Peel Resistance]

The prepared composition was coated on a silicon wafer (substrate) by a rotation coating method. Subsequently, under an atmospheric atmosphere, heating (firing) was performed at the heating temperature (° C.) and heating time (sec) shown in Table 2 below to form a film having an average thickness of 150 nm to obtain a film-equipped substrate with a film formed on the substrate. The substrate with the film was immersed in an alkaline hydrogen peroxide solution (25 mass% aqueous ammonia solution / 30 mass% hydrogen peroxide solution / water = 1/2/40 (mass ratio) in a mixed solution (SC1) at 60 to 65 ° C.) for 5 minutes. , Washed, dried. The average thickness of the membrane before and after immersion was measured. Assuming that the average thickness of the film before immersion is T ₀ and the average thickness of the film after immersion is T ₁ , the absolute value of the value obtained from (T ₁ -T ₀ ) × 100 / T ₀ was calculated, and the film thickness change rate (%) was used. . Wet peel resistance was evaluated as "A" (good) when the film thickness change rate was less than 5%, and "B" (bad) when it was 5% or more.

[Bending resistance]

The prepared composition was coated on a silicon substrate on which a thermal oxide film having an average thickness of 500 nm was formed by rotational coating, and then heated (fired) at 350 ° C. for 60 seconds in an atmospheric atmosphere to form a film having an average thickness of 200 nm. Obtained substrates were obtained. On the obtained film-equipped substrate, a composition for forming a silicon-containing film ("NFC SOG080" by JSR Co., Ltd.) was coated by a rotational coating method, followed by heating (firing) at 200 DEG C for 60 seconds in an atmospheric atmosphere, and then adding The furnace was heated (fired) at 300 ° C for 60 seconds to form a silicon-containing film having an average thickness of 50 nm. Subsequently, an ArF resist composition ("AR1682J" by JSR Co., Ltd.) was coated on the silicon-containing film by a rotational coating method, and heated (fired) at 130 ° C for 60 seconds in an atmospheric atmosphere to obtain an average thickness of 200 nm. A resist film was formed. Then, the resist film was interposed using a Nikon ArF excimer laser exposure apparatus (lens numerical aperture 0.78, exposure wavelength 193 nm) through a one-to-one line-and-space mask pattern with a target size of 100 nm. , After exposure by changing the exposure amount, heated (fired) at 130 ° C. for 60 seconds in an atmospheric atmosphere, developed at 25 ° C. for 1 minute using a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution, and washed with water, By drying, a substrate on which a line and space resist pattern having a pitch of 200 nm having a line width of 30 nm to 100 nm was formed was formed.

Using the resist pattern as a mask, using an etching apparatus ("TACTRAS" of Tokyo Electron Co., Ltd.), CF ₄ = 200sccm, PRESS. = 85mT, HF RF (high frequency power for plasma generation) = 500W, LF RF ( The silicon-containing film was etched under the conditions of high frequency power for bias) = 0 W, DCS = -150 V, RDC (gas center flow rate ratio) = 50% to obtain a substrate on which a pattern was formed on the silicon-containing film. Subsequently, using the silicon-containing film pattern as a mask, using an etching apparatus ("TACTRAS" of Tokyo Electron Co., Ltd.), O ₂ = 400 sccm, PRESS. = 25 mT, HF RF (high frequency power for plasma generation) = 400 W , The film was etched under the conditions of LF RF (high frequency power for bias) = 0 W, DCS = 0 V, and RDC (gas center flow rate ratio) = 50% to obtain a substrate on which a pattern was formed on the film. Using the film pattern as a mask, using an etching device ("TACTRAS" of Tokyo Electron Co., Ltd.), CF ₄ = 180sccm, Ar = 360sccm, PRESS. = 150mT, HF RF (high frequency power for plasma generation) = 1,000 The thermal oxide film was etched under conditions of W, LF RF (high frequency power for bias) = 1,000 W, DCS = -150 V, RDC (gas center flow rate) = 50%, and 60 sec.

Thereafter, the shape of the film pattern of each line width is enlarged by 250,000 times with a scanning electron microscope ("CG-4000" by Hitachi High-Technologies Co., Ltd.) to obtain an image enlarged by 250,000 times, and the image processing thereof is shown in Fig. 2. As described above, the position Xn (n = 1 to 1) in the line width direction measured at 10 positions at 100 nm intervals with respect to the transverse side surface 3a of the film pattern 3 (line pattern) having a length of 1,000 nm in the observed shape. 10) and the value of 3 sigma obtained by doubling the standard deviation calculated from the position Xa of the average value of the positions in the line width direction was referred to as LER (line edge roughness). The LER indicating the degree of curvature of the film pattern increases as the line width of the film pattern becomes thin. The flexural resistance is `` A '' (good) when the line width of the film pattern in which the LER is 5.5 nm is less than 40.0 nm, `` B '' (somewhat good) when 40.0 nm or more and less than 45.0 nm, and 45.0 nm or more when `` C ”(poor). Incidentally, the curvature state of the film pattern shown in FIG. 2 is described to be more exaggerated than the actual one.

As can be seen from the results in Table 2, the composition of the Examples and the substrate with a film are excellent in flatness, wet peel resistance and bending resistance of the pattern while maintaining solvent resistance. On the other hand, although the composition and the film-equipped substrate of the comparative example had excellent solvent resistance, the flatness and the bending resistance of the pattern were poor, and the wet peel resistance was also low.

The composition of the present invention can form a film excellent in flatness, wet peeling resistance and pattern bending resistance while maintaining solvent resistance. The film of the present invention is excellent in flatness, wet peeling resistance and bending resistance of the pattern while maintaining solvent resistance. According to the film forming method of the present invention, a film excellent in flatness, wet peeling resistance and pattern bending resistance can be formed while maintaining solvent resistance. According to the method for manufacturing a patterned substrate of the present invention, a good patterned substrate can be obtained by using the formed excellent film. Therefore, these can be suitably used for the manufacture of semiconductor devices, etc., which are expected to be further refined in the future.

1: Silicon substrate
2: membrane
3: Membrane pattern
3a: Transverse side of membrane pattern

Claims (12)

A compound having a group represented by the following formula (1), a molecular weight of 200 or more, and a content of carbon atoms of 40 mass% or more,
menstruum
The composition containing.

(In formula (1), R ¹ and R ² are each independently a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or these groups are combined with each other) These are part of the alicyclic structure of reduced water 3 to 20 composed of the carbon atom to which they are attached Ar ¹ is a group excluding (n + 3) hydrogen atoms from arenes or heteroarene of reduced water 6 to 20. X is an oxygen atom ^{, -CR 3 R 4 -, -CR} 3 R 4 -O- , or -O-CR ³ R ⁴ -. a R ³ and R ⁴ are, each independently, a hydrogen atom, a fluorine atom, a C 1 -C 20 monovalent It is a hydrocarbon group or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or these groups are part of an alicyclic structure of reduced water 3 to 20 composed of carbon atoms to which they are bonded to each other, where n is an integer from 0 to 9. n If a person, R ⁵ is a hydroxy group, to A gen atom, a nitro group or a monovalent organic group having 1 to 20 carbon atoms. N not less than 2, a plurality of R ⁵ are the same or different and are a hydroxy group, a halogen atom, a nitro group, or a monovalent group having 1 to 20 carbon atoms with each other It is an organic group or is a part of a ring structure of reduced water 4 to 20 composed of an atom chain to which two or more of a plurality of R ⁵ are joined together to combine them. * Is represented by the formula (1) in the compound. It indicates the binding site with a part other than the group to be.) The composition according to claim 1, wherein the compound has a group represented by formula (1) of 2 or more. The composition according to claim 1 or 2, wherein the arene in Ar ¹ of formula (1) is benzene or naphthalene. The composition according to any one of claims 1 to 3, wherein the compound has a molecular weight of 2,000 or less. The composition according to any one of claims 1 to 4, wherein X in the formula (1) is an oxygen atom. The composition according to any one of claims 1 to 5, wherein the content of hydrogen atoms in the compound is 6.5% by mass or less. The composition according to any one of claims 1 to 6 for forming a resist underlayer film. A film formed of the composition according to any one of claims 1 to 7. A step of coating a composition containing a compound having a group represented by the following formula (1), a molecular weight of 200 or more and a content of carbon atoms of 40% by mass or more, and a solvent on at least one side of the substrate;
Process for heating the coating film formed by the coating process
Method of forming a film comprising a.

(In formula (1), R ¹ and R ² are each independently a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or these groups are combined with each other) These are part of the alicyclic structure of reduced water 3 to 20 composed of the carbon atom to which they are attached Ar ¹ is a group excluding (n + 3) hydrogen atoms from arenes or heteroarene of reduced water 6 to 20. X is an oxygen atom ^{, -CR 3 R 4 -, -CR} 3 R 4 -O- , or -O-CR ³ R ⁴ -. a R ³ and R ⁴ are, each independently, a hydrogen atom, a fluorine atom, a C 1 -C 20 monovalent It is a hydrocarbon group or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or these groups are part of an alicyclic structure of reduced water 3 to 20 composed of carbon atoms to which they are bonded to each other, where n is an integer from 0 to 9. n If a person, R ⁵ is a hydroxy group, to A gen atom, a nitro group or a monovalent organic group having 1 to 20 carbon atoms. N not less than 2, a plurality of R ⁵ are the same or different and are a hydroxy group, a halogen atom, a nitro group, or a monovalent group having 1 to 20 carbon atoms with each other It is an organic group or is a part of a ring structure of reduced water 4 to 20 composed of an atom chain to which two or more of a plurality of R ⁵ are joined together to combine them. * Is represented by the formula (1) in the compound. It indicates the binding site with a part other than the group to be.) A step of coating a composition containing a compound having a group represented by the following formula (1), a molecular weight of 200 or more and a content of carbon atoms of 40% by mass or more, and a solvent on at least one side of the substrate;
A process of heating the coating film formed by the coating process at a temperature of 300 ° C or higher
Method of forming a film comprising a.

(In formula (1), R ¹ and R ² are each independently a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or these groups are combined with each other) These are part of the alicyclic structure of reduced water 3 to 20 composed of the carbon atom to which they are attached Ar ¹ is a group excluding (n + 3) hydrogen atoms from arenes or heteroarene of reduced water 6 to 20. X is an oxygen atom ^{, -CR 3 R 4 -, -CR} 3 R 4 -O- , or -O-CR ³ R ⁴ -. a R ³ and R ⁴ are, each independently, a hydrogen atom, a fluorine atom, a C 1 -C 20 monovalent It is a hydrocarbon group or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or these groups are part of an alicyclic structure of reduced water 3 to 20 composed of carbon atoms to which they are bonded to each other, where n is an integer from 0 to 9. n If a person, R ⁵ is a hydroxy group, to A gen atom, a nitro group or a monovalent organic group having 1 to 20 carbon atoms. N not less than 2, a plurality of R ⁵ are the same or different and are a hydroxy group, a halogen atom, a nitro group, or a monovalent group having 1 to 20 carbon atoms with each other It is an organic group or is a part of a ring structure of reduced water 4 to 20 composed of an atom chain to which two or more of a plurality of R ⁵ are joined together to combine them. * Is represented by the formula (1) in the compound. It indicates the binding site with a part other than the group to be.) A step of coating a composition containing a compound having a group represented by the following formula (1), a molecular weight of 200 or more and a content of carbon atoms of 40% by mass or more, and a solvent on at least one side of the substrate;
A step of heating the coating film formed by the coating process;
Forming a silicon-containing film on a surface side opposite to the substrate of the film formed by the heating process;
Process of removing the silicon-containing film with a basic liquid
Method of manufacturing a patterned substrate comprising a.

(In formula (1), R ¹ and R ² are each independently a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or these groups are combined with each other) These are part of the alicyclic structure of reduced water 3 to 20 composed of the carbon atom to which they are attached Ar ¹ is a group excluding (n + 3) hydrogen atoms from arenes or heteroarene of reduced water 6 to 20. X is an oxygen atom ^{, -CR 3 R 4 -, -CR} 3 R 4 -O- , or -O-CR ³ R ⁴ -. a R ³ and R ⁴ are, each independently, a hydrogen atom, a fluorine atom, a C 1 -C 20 monovalent It is a hydrocarbon group or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or these groups are part of an alicyclic structure of reduced water 3 to 20 composed of carbon atoms to which they are bonded to each other, where n is an integer from 0 to 9. n If a person, R ⁵ is a hydroxy group, to A gen atom, a nitro group or a monovalent organic group having 1 to 20 carbon atoms. N not less than 2, a plurality of R ⁵ are the same or different and are a hydroxy group, a halogen atom, a nitro group, or a monovalent group having 1 to 20 carbon atoms with each other It is an organic group or is a part of a ring structure of reduced water 4 to 20 composed of an atom chain to which two or more of a plurality of R ⁵ are joined together to combine them. * Is represented by the formula (1) in the compound. It indicates the binding site with a part other than the group to be.) A step of coating a composition containing a compound having a group represented by the following formula (1), a molecular weight of 200 or more and a content of carbon atoms of 40% by mass or more, and a solvent on at least one side of the substrate;
A step of heating the coating film formed by the coating process;
Forming a silicon-containing film on a surface side opposite to the substrate of the film formed by the heating process;
Forming a resist pattern on a surface side opposite to the substrate of the silicon-containing film;
Etching using the resist pattern as a mask
Method of manufacturing a patterned substrate comprising a.

(In formula (1), R ¹ and R ² are each independently a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or these groups are combined with each other) These are part of the alicyclic structure of reduced water 3 to 20 composed of the carbon atom to which they are attached Ar ¹ is a group excluding (n + 3) hydrogen atoms from arenes or heteroarene of reduced water 6 to 20. X is an oxygen atom ^{, -CR 3 R 4 -, -CR} 3 R 4 -O- , or -O-CR ³ R ⁴ -. a R ³ and R ⁴ are, each independently, a hydrogen atom, a fluorine atom, a C 1 -C 20 monovalent It is a hydrocarbon group or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or these groups are part of an alicyclic structure of reduced water 3 to 20 composed of carbon atoms to which they are bonded to each other, where n is an integer from 0 to 9. n If a person, R ⁵ is a hydroxy group, to A gen atom, a nitro group or a monovalent organic group having 1 to 20 carbon atoms. N not less than 2, a plurality of R ⁵ are the same or different and are a hydroxy group, a halogen atom, a nitro group, or a monovalent group having 1 to 20 carbon atoms with each other It is an organic group or is a part of a ring structure of reduced water 4 to 20 composed of an atom chain to which two or more of a plurality of R ⁵ are joined together to combine them. * Is represented by the formula (1) in the compound. It indicates the binding site with a part other than the group to be.)

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